Process for the continuous dyeing and printing of fibre material from linear,high molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols



United States Patent 3,510,243 PROCESS FOR THE CONTINUOUS DYEING ANDPRINTING OF FIBRE MATERIAL FROM LIN- EAR, HIGH MOLECULAR ESTERS OF ARO-MATIC POLYCARBOXYLIC ACIDS WITH POLY- FUNCTIONAL ALCOHOLS Marcel Seuret,St. Kilda, Melbourne, Victoria, Australia, and Willi Leutenegger,Bottmingen, Basel-Land, and Hans E. Wegmuller, Riehen, Switzerland,assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. Filed Dec.1, 1966, Ser. No. 598,184 Int. Cl. C09b 1/00, 5/62 US. Cl. 839 13 ClaimsABSTRACT OF THE DISCLOSURE A process for the continuous dyeing orprinting of fiber material from linear, high molecular esters ofaromatic polycarboxylic acids with polyfunctional alcohols, is provided.There is applied to the fiber material a solution of (A) a mixture ofsolvents consisting essentially of (a) 50 to 99% by weight of awater-insoluble chlorinated hydrocarbon having a boiling point between50 and (b) 50 to 1% by weight of a liquid, water-soluble, or-

ganic solvent having a boiling point below 220 C., and

(B) a dispersion dyestulf, e.g. anthroquinone.

The resulting dyeing or print on the fiber material is then fixed bysubjecting the treated fiber material ,to a subsequent heat treatment attemperatures from about 130 C. to below the softening point of the fibermaterial.

The present invention concerns a process for the continuous dyeing andprinting of fibre material from linear, high molecular esters ofaromatic polycarboxylic acids with polyfunctional alcohols, the dyeliquor used therefor, as well as the fibre material dyed or printed bythis process.

As it is known, linear, high molecular esters of aromatic polycarboxylicacids with polyfunctional alcohols are dyed with aqueous dyestuffdispersions either from a long bath at the boiling point of the waterand in the presence of so-called carriers, or at temperatures of 100 to150 C. under pressure, or by impregnating with an aqueous, thickeneddyestuff dispersion, drying, thermofixing the dyestulf on this materialand, finally, washing out the thickener and dispersing agent. Thesedyeing processes, however, have several disadvantages: one is that thedispersion dyestuffs must be brought into a finely dispersed form Whicshnecessitates time-consuming milling operations with suitable dispersingagents, and also they cause great amounts of waste water so thatcomprehensive purification of waste water is necessary.

This led to the idea of dyeing the material mentioned above with organicdyestuif solutions. One suggestion is to treat polyethylene glycolterephthalate films with a solution or dispersion of disperse dyestuffsin a solvent which wets the polyethylene glycol terephthalate and thento subsequently fix the dyestuif on this material by a heat treatment.Methylethyl ketone, benzyl alcohol, toluene, methyl isobutyl ketone,anisol, ethyl acetate, cyclohexanone and a mixture of dimethyl acetamideand methylethyl ketone are mentioned as solvents.

This process, however, is unsuitable for the dyeing of polyethyleneglycol terephthalate textile material, as generally, dull and weaklycoloured dyeings are obtained.

A process has now been found by which fibre material from linear, highmolecular esters of aromatic polycar- 3,510,243 Patented May 5, 1970boxylic acids with polyfunctional alcohols, particularly polyethyleneglycol terephthalate fibres, can be continuously dyed and printed. Thenew process consists in applying to said fibre material a solutioncomprising a mixture of solvents consisting essentially of (a) 50 to 99percent by weight of unhalogenated or halogenated hydrocarbon having aboiling point between 50 and 150 C.;

(b) 50 to 1 percent by weight of a liquid, water-soluble, organicsolvent having a boiling point below 220 C., and

(c) a dispersion dyestuif soluble in said mixture, in a sufiicientamount to impart to said fibre material in a desired color depth,

and also, if necessary, a thickener, removing a substantial part ofexcess dye liquor from the material and fixing the resulting dyeing orprint on said fibre material by subjecting the treated fibre material toa subsequent heat treatment at temperatures below the softening point ofthe fibre material.

Surprisingly deep, brilliant dyeings which are fast to rubbing areobtained by this process without after-soaping thereof. Their brilliancyis completely equal to that of dyeing attained by the usual processeswith aqueous dispersions and their depth of shade is, in some cases,even superior. The time consuming milling operations necessary to attaina fine distribution of the dyestuffs are unnecessary. Also, the mixturesof solvents to be used according to the invention can easily be regainedand used again in the dyeing process; moreover, in contrast to thepreviously known processes all refining of waste Water becomessuperfluous as the after-soaping in rinsing baths which has been usualhitherto is not necessary.

Suitable hydrocarbons boiling between 50 and 150 C. which can be used ascomponent (a) of mixtures of solvents usable according to the inventionare, e.g. aromatic hydrocarbons such as toluene or xylene; preferablyhowever, these mixtures of solvents contain 50 to 99 percent by weightof halogenated, particularly chlorinated, hydrocarbons, e.g.chlorobenzene, mainly however, low aliphatic halogenated hydrocarbonssuch as chlorinated hydrocarbons, e.g. chloroform, carbon tetrachloride,trior tetra-chloroethylene (perchloroethylene), tetrachloroethane ordibromoethylene. Also mixtures of such solvents can form the waterinsoluble component of mixtures of solvents usable according to theinvention.

By liquid, water soluble, organic solvents boiling below 220 C. (b) aremeant thermostable solvents which are water soluble not only tofractions of percentages but to some percentages. Examples thereof arebenzyl alcohol, cyclohexanone, cyclohexanol, n. and sec. butyl alcoholor methylethyl ketone. Preferred, however, are those solvents as definedwhich are miscible with water in any ratio. Examples thereof are:monovalent low aliphatic alcohols such as, e.g. methanol, ethanol andnor isopropanol; alkylene glycol monoalkyl ethers such as ethyleneglycol monomethyl 0r monoethyl ether; then also furfuryl alcohol ortetrahydrofurfuryl alcohol; or divalent aliphatic alcohols such asethylene glycol 0r 1,2-propylene glycol; also low aliphatic ketones suchas acetone; low cyclic ethers such as dioxane; also amides of low fattyacids such as dimethyl formamide or dimethyl acetamide; then carbonicacid amides, such as tetrarnethyl urea; or tertiary organic amines suchas pyridine; as Well as mixtures of such organic solvents.

Mixtures of solvents are preferred which consist of to 99 percent byweight of chlorinated lower aliphatic hydrocarbon boiling between 50 andC. and of 20 to 1 percent by weight of an organic solvent boiling below220 C. which is water-miscible in any ratio. In particular,

3 mixtures of 90 percent by weight of perchloroethylene ortrichloroethylene and 10 percent by weight of methanol ortetrahydrofurfuryl alcohol are suitable.

The composition of the mixture of solvents depends on the solubility ofthe dyestuff or mixture of dyestuffs to be to the invention; for examplethe dyeings are fast to dry cleaning, perspiration and rubbing.

The following examples illustrate the invention. The temperatures aregiven in degrees centigrade.

used. Preferably homogeneous clear dyestuif solutions are 5 EXAMPLE 1used.

Dispersion dyestuffs usable according to the invention of dyestuff 0fthe formula can belong to any classes of dyestuffs desired. They are, inparticular, metal-free azo dyestuffs, also anthraquinone, 10 nitro,methine, styrene, azostyrene, naphthoperinone, C-H so2- N: 3quinophthalone or naphthoquinone imine dyestuffs, which I 1 i are freefrom water solubilising groups which dissociate N02 HiN acid in water.

Depending on the desired depth of shade, the dyestuff solution to beused according to the invention contains 0.1 to 10 percent by Weight ofone or more of the dyestuffs mentioned.

If necessary, the dye solution usable according to the invention canalso contain thickeners, advantageously those which are soluble in thedefined mixture of solare {hssolved In 1000 of a mlXture 0f olventswhich vents, e.g. thickeners having a basis of cellulose ester orCohslsts of 90 Pemeht y Weight of pefehlofoethylene and polyvinyl l l oresten 10 percent by weight of methanol. The solution is clari- The fibrematerial as defined is impregnated, e.g. by h e by filtratioh-Polyethylene glycol terephthalate fabric printing or spraying,preferably however, by pad dyeing 1s impregnated at room temperaturewith this clear, yelin the foulard. In the latter case, the fibrematerial is con- 10w dye sohlhoh, the lmpreghated fabric is Squeezed outtinuously passed h h h dy stufi l i d to about 100 percent content ofsolution (calculated on tageously at room temperature, then squeezed outto the the y Weight of the goods) and dfled t 0 t 80 C- desired contentof impregnation solution of about to The'impfegnated and dried r c isthen thermOfiXed for 150 percent by weight (calculated on the dry weightof 30 3 mlnllies at 220 C. the goods). The main part of the mixtur ofsolvents A strongly coloured, level, brilliant and well developedmaining in the fibre material is then removed, advangold-yellow y g i8Obtainedtageously under mild conditions at 40 to C., par- If, m theabove mixture of solvents, the p t y ti l l i a warm, dry ir t Th d tfl? i th n ene is replaced by the same amount of toluene or dibrofixedby a subsequent heat treatment on the still moist or 35 moethylene andotherwise the procedure described in this optionally already dried fibrematerial either by steame a p e 18 followed, then dyeings of similarquality are ing, preferably under pressure at about C., or by a btainddry heat treatment at a temperature of at least C. If, n the above mixr of v n h perchl rabut below the softening point of the fibre material.These ethylene and methanol are used in a weight ratio of 80:20 twotypes of heat treatment can also be combined, but 40 instead of 90:10,then with otherwise the same procedure, the dry heat treatment, theso-called thermofixing, is presimilar results are obtained. ferred.Contact heat, a treatment with high frequency If, instead of thedyestuff mentioned in the example, alternating currents or infraredirradiation is suitable for the same amount of one of the dyestuffsgiven in column this purpose; preferably, however, the dyestuif is fixed2 of the following Table I is used and otherwise the proon the fibrematerial in a hot airstream at 180 to 230 C., 45 cedure given in theexample is followed, then strongly particularly at a temperature of 200to 220 C. coloured, level and well developed dyeings on polyethyl-Level, strongly coloured and fast dyeings are obtained ene glycolterephthalate are obtained of the shades given on the fibre materialmentioned by the process according in column 3 of this table.

TABLE I Shade on olyethylene glycol Example No. Dyestufi terephthalate 2Blue.

o NH-CH3 CzHs Q Q 3 OzN- N=N N Red.

\CH2CH2CN CgH5 Q G 4 O2N- N=N N Blulsh red.

l \CH2CH2OH CH3 Violet.

5. 02N-N=NN(CH2OH2OH)2 7 EXAMPLE 17 5 g. of the dyestuff of the formulaare dissolved in 1000 g. of a mixture of solvents which consists of 85percent by weight of trichloroethylene and 15 percent by weight ofmethanol. After clarifying the solution, polyethylene glycolterephthalate fabric is impregnated and dried as described in Example 1.The impregnated and dried fabric is then thermofixed for 90 seconds at200 C.

A strongly coloured, level and well developed red dyeing is obtained.

If, instead of -85 percent by weight of trichloroethylene, the sameamount of perchloroethylene and/or instead of 15 percent by weight ofmethanol, the same amount of benzyl alcohol is used and otherwise theprocedure given in the example is followed, then similar results areobtained.

If the impregnated and dried fabric is not thermofixed but steamed at130 for 1 minutes under pressure, then similar good results areobtained.

EXAMPLE l8 7 g. of the dyestuff of the formula are dissolved in 1000 g.of a mixture of solvents which consists of 90 percent by weight ofchloroform and 10 percent of weight of ethanol and this solution isclarified. A polyethylene glycol terephthalate fabric is impregnatedwith the clear red dye solution and dried as described in Example 1. Theimpregnated and dried material is then thermofixed for 5 minutes at 190C.

A level and intensively red dyeing is obtained.

If, instead of chloroform, the same amount of trichloroethylene,perchloroethylene and/ or instead of ethanol, the same amount ofmethanol, tetrahydrofurfuryl alcohol, isopropanol or dimethyl formamideis used and otherwise the procedure given in the example is followed,then dyeings having similar good properties are obtained.

If a mixture of solvents consisting of 50 percent by weight ofperchloroethylene and 50 percent by weight of methanol is used andotherwise the procedure given in the example is followed, then a leveland intensively red dyeing is also obtained.

EXAMPLE 19 CzHa CH2CH2OH CzHa CHzCHzOH 6 g. of the dyestuif of theformula are dissolved in 1000 g. of a mixture of solvents which consistsof 90 percent by weight of chlorobenzene and 10 percent by weight ofmethanol and the solution is clarified.

A fabric made from polyethylene glycol terephthalate is impregnated withthis clear violet solution and dried as described in Example 1 andthermofixing of the impregnated and dried fabric is then performed for 2minutes at 210 C.

A level and strongly coloured violet dyeing is obtained.

8 EXAMPLE 20 5 g. of the dyestuflf of the formula NH-CO CH are dissolvedin -0 g. of a mixture of solvents which consists of 97 percent by weightof perchloroethylene and 3 percent by weight of dimethyl formamide andthe solution is clarified. Polyethylene glycol terephthalate fabric isimpregnated with this solution and dried as described in Example 1. Theimpregnated and dried fabric is then thermofixed for 4 minutes in a hotairstream at 200 C.

A level and strongly coloured violet dyeing is obtained.

If, in the mixture of solvents given above, the dimethyl formamide isreplaced by the same amount of ethylene glycol monomethyl or monoethylether or by pyridine, then with otherwise the same procedure, similarresults are obtained.

EXAMPLE 21 5 g. of the dyestufl? of the formula CHaOHzOH are dissolvedin 1000 g. of a mixture of solvents which consists of 95 percent byweight of perchloroethylene and 5 percent by weight of dimethylacetamide and the solution is clarified. A polyethylene glycolterephthalate fabric is impregnated with this solution and dried asdescribed in Example 1. The impregnated and dried fabric is thenthermofixed at 200 C. for '90 seconds with an apparatus for infraredirradiation.

A brilliant, level red dyeing is obtained.

We claim:

1. A process for the continuous dyeing or printing of fiber materialfrom linear, high molecular esters of aromatic polycarboxylic acids withpolyfunctional alcohols, comprising:

(1) applying to said fiber material a solution consisting essentially of(A) a mixture of solvents consisting essentially of (a) 5099 percent byweight of a water-insoluble chlorinated hydrocarbon having a boilingpoint between 50 and 150 C.;

(b) 50-1 percent by weight of a liquid, watersoluble, organic solventhaving a boiling point below 220 C. and selected from the groupconsisting of monovalent aliphatic alcohols having from 1 to 4 carbonatoms, ethylene glycol monomethyl or monoethyl ether, fur-furyl alcohol,tetrahydrofurfuryl alcohol, ethylene glycol, 1,2-propylene glycol,acetone, dioxane, dimethyl formamide, dimethyl acetamide, tetramethylurea, pyridine, benzyl alcohol, cyclohexanone, cyclohexanol ormethylethyl ketone, or mixtures of these solvents, and

(B) a dispersion dyestuif, and (H) fixing the resulting dyeing or printon said fiber material by subjecting the-treated fiber material to asubsequent heat treatment at temperatures from about C. to below thesoftening point of the fiber material.

2. A process as described in claim 1, wherein said component (a) is achlorinated lower aliphatic hydrocarbon having a boiling point between50 and C.

3. A process as described in claim 1, wherein said component (a) isperchloroethylene or trichloroethylene.

4. A process as described in claim 1, wherein said component (b) ismethanol or tetrahydrofurfuryl alcohol.

5. A process as described in claim 1, wherein said dispersion dyestuffis a metal-free azo dyestuif.

6. A process as described in claim 1, wherein said dispersion dyestufiis an anthraquinone dyestuif.

7. A process as described in claim 1, wherein dispersion dyestuff is anitro dyestuif.

8. A process as described in claim 1, wherein dispersion dyestuff is astyrene dyestuff.

9. A process as described in claim 1, wherein said dispersion dyestuffis a naphthoquinoneimino dyestuff.

10. A process as described in claim 1, wherein in step (I) said fibermaterial is impregnated with said non-aqueous solution.

11. A process as described in claim 1, wherein in step (11) said dyeingis fixed by heat treating the impregnated fiber material in dry air at atemperature of from at least 180 C. to a temperature below the softeningpoint of the fiber material.

12. A process as described in claim 1, wherein said fiber materialconsists essentially of polyethylene glycol terephthalate fibers.

13. Fiber material from linear, high molecular esters of aromaticpolycarboxylic acids with polyfunctional alcohols, dyed or printed bythe process described in claim 1,

said

said

1 0 References Cited UNITED STATES PATENTS 2,274,751 3/1942 Sowter et al8-94 X 3,129,053 4/1964 Castle 893 FOREIGN PATENTS 2/1963 Great Britain.

OTHER REFERENCES GEORGE F. LESMES, Primary Examiner T. J. HERBERT, JR.,Assistant Examiner US. Cl. X.R.

